Catalyst purification



Nov. 15, 1949 1 l. sRlFFlN, JR Y 2,487,867

cATALYsT PURIFIcATIoN Filed July 11, 1945 Dm! CA-rAmrs-r 1 Tc Rama-rom Lindsaq' Gn'ff1`r1A,Jr. Urn/sabor' l bq Clt-borne@ Patented Nov. 15, 17949 CATALYST PURIFICATION Lindsay I. Griffin, Jr., Baton Rouge, La., assgnor to Standard 0il Development Company, a corporation of Delaware Application July 11, 1945, Serial N0. A604,349

The normal features of my invention are fully disclosed in vthe following specification Yand claims considered in connection with the `accompanying drawing.

The object vof my invention is to purify .and reactivate .a catalyst employed in the synthesis of hydrocarbons from CO and hydrogen in an eicient Iand .expeditious manner. t

In the .synthesis of normally liquid hydrocarbons from VCO and hydrogen, .there is unavoidably formed on the catalyst aquantity of .oilyand waxy material which impairs the activity of the catalyst, and therefore, requires periodic treatment of the catalyst te remove said waxyand oily deposits. In brief, my invention involves subjecting such contaminated catalysts to destructive hydrogenation followed by treatment with a wash solvent, all of which will appear `more fully and at large hereinafter. The -hydrogenation of the contaminants maybe readily effected since the metals of the iron group which constitute a part of the hydrocarbon synthesis catalyst are also very effective for the 'hydrogenation of hydrocarbons. `v

In the accompanying drawing, I have shown flow plan which illustrates a preferred method of carrying my improvements into .practical effect.

Referring in detail to the drawing,V I have shown a hindered settler reactor 2 containing a body of fluidized catalyst, that is tosay, .a mass Aof powdered Icatalyst suspended `in the reaction gases or vapors. This type of reactor is known in the catalytic cracking art, Vand the method of its operation need not be fully explained `herein, for it does not go to the heart of my invention. It will be suflicient merely to point yout that the synthesis gases, consisting Iof C and hydrogen properly proportioned, are charged by line I to reactor 2 where they contact the catalyst C (which may be cobalt activated by -thoria and carried on kieselguhr, or alternatively, it may be an iron catalyst), under proper conditions of temperature and pressure and for a sufdcient period of time to effect the desired conversion. Whereupon, a product for recovery is taken on overhead through line 6 and recovered and treated in a known manner;L It is indicated Eduring the reaction, that oily and waxy materials -form on the catalyst, and according to my invention, I withdraw the powdered catalyst through a bottom .drawoi pipe 3 carrying aiiow control valve 5. Of course, it will fbe understood that an equal quantity of `catalyst `must be fed to the reactorV to replace that withdrawn, .and this catalyst may be padded with .the synthesis gas 6 Claims. (Cl. 260-449.'6)

entering through line I. Referring again to drawoff pipe 3, the same is provided in a known manner with a plurality of taps 4 through which a small quantity of gaseous material such as inert hydrocarbon, portion of the synthesis gas, or the like, may be forced into the downilow stream of catalyst t0 increase the k.fluid `:Ilow thereof, and to prevent bridging or plugging of the catalyst in the pipe. The catalyst discharges into a stream of hydrogenor hydrogen-containing gas, the latter `being introduced through pipe 9, heated in the ired'coil I'I, and thence pumped by pump I4 through 'line I5 into line 3 and thence into a hydrogenation reactor I6 lwherein it forms a dense suspension of catalyst in the hydrogencontaining gas similar to that in reactor v2. This uid condition may be achieved, as is known, by regulating the linear velocity of the gasiform material controlled within the limits of 1A to 10 feet per second, preferably however, vfrom 1/2 to 3 feet per second. 'The -conditions of temperature and pressure will be set forth hereinafter, but for the present it will simply be stated that the waxy material contained on the catalyst is subjected to known conditions of temperature and pressure for a suiiicient period of time to effect a substantial amount of destructive hydrogenation to form certain volatile products which are Withdrawn overhead through 'line I1V and to lower the molecular weight and/or viscosities of the oily material and wax remaining on the catalyst, and also to make it more pervious or porous, so that it will be more adaptable for effective treatment with the Wax solvent to remove it from the catalyst. The volatile material in line I'1 is forced through .a condensing coil I8, and thence discharged into a separation drum I9, from which the hydrogen-containing gas is withdrawn overhead through line 22. Since this gas will be associated .normally with hydrocarbon gases, it is advisable to scrub the said gas with .a light naphtha or other scrubbing oil in S, for the purpose of dissolving out substantial quantities of the said hydrocarbons, and thus, purifying the hydrogen stream, whereupon the major part of the hydrogen stream is4 then recycled to line :9 for further use in the process. Aminor amount of the gas in line 22 is rejected from the system.

Meanwhile, the catalyst is withdrawn from hydrogenator I6 through a-drawoff pipe 20 carrying a iiow control valve 22, and also gas introducing leads 2-I performing the same function as taps 4 in line 3, 1and the thus withdrawn catalyst is discharged into a mixer 30 where it is mixed with a .solvent for the wax such as, for ex- 3 ample, a naphtha fraction, the mixer being provided with a suitably driven mixing means 32 to provide agitation, and therefore, good contact between the liquid solvent and the catalyst. The solvent is introduced through line 35; however, another portion of solvent is introduced into the bottom of an extraction tower 40 through line 39 and passes upwardly against the catalyst which iows downwardly from mixer 30 to a sump or well 42. Thus, the catalyst is subjected t a countercurrent solvent wash. In order to provide more intimate Contact between the catalyst and., the liquid solvent, extraction tower 40 is provided with a plurality of baiesM, Which Cause'thef It making access Vof solvent into the pores more easily accomplished.

catalyst to follow a tortuous'pathinv passing from mixer 30 to sump 42. A slurry of catalyst and solvent is withdrawn from well 42'throughline D, and after heating in 52 is discharged into'a in the Solvent separation drum 53 from which the solvent is ,taken off overhead as a vapor, thence condensed charged into a fractional distillation column 'E3 from which the solvent, substantially free of wax and oily materialoriginally on the catalyst, is recovered overhead through line 'i5 and cooled in the condenser 18 and returned to solvent storage 60 for further use in the process. The oilyv and waxy bottoms are rejected from the system through line 80.

Referring again to the separation drum IS, the hydrocarbon bottoms withdrawn through line 23 may be processed to recover valuable hydrocarbons.

In the foregoing description, I have set forth the essentials of an operation in which a powdered catalyst employed in a fluid solids type of operation was purified. Of course, my improvements extend also in their broadest aspect to successive hydrogenation and solvent treatment of any fouled catalyst contaminated with waxy and oil deposits and containing an active hydrogenating constituent, regardless of the physical form of the catalyst or the type of operation in which it is employed. Thus,'if reactor 2 were a stationary bed type of reactor where the catalyst in the form of pills, pellets, granules, etc., is supported on a foraminous support of some sort, the catalyst may be purified by periodically discontinuing the productive phase of the process, and thereafter treating the catalyst phase with hydrogen to destructively hydrogenate the deposits on the catalyst, and after that, the catalyst may be Temp. in F. using cobalt type catalyst degrees 360 to 500 Press. in lbs/sq. in. (gauge) 0 to 300 Temp. inF. using iron type catalyst degrees-- Y4501370 750 Press. in lbs/sq. in. `(gauge) V tor'750 `Preferred 25 to 350 As to the solvent, any cheap hydrocarbon solvent is satisfactory such as naphtha, gasoline,

4 and liquified normally gaseous hydrocarbons. To recapitulate briey, my invention involves cleaning and/or reactivating a catalyst employed in hydrocarbon synthesis, which catalyst has become contaminated with waxy and/or oily deposits. The process involves first subjecting the fouled catalyst to ak destructive hydrogenation, and thereafter to a solvent treatment. The destructive hydrogenation improves the efficiency of the subsequent solvent treatment for the following 't reasons:

(l)v Thevpores within the catalyst particle are partially freed ofA wax by hydrogenation thus (2) The lowered viscosity and melting point of the wax favors a more rapid solution of the wax After the catalyst isA freed of wax, it may be `returnedto thev reactor in the dry powdered state or it may be returned as a slurry or in any other form that is convenient.

What I claim is;

1. The method of 4removing continuously and uninterruptedly oilyand waxy deposits from a Yiluidizable solid catalyst selected from a class consisting of iron and cobalt employed in the synthesis of hydrocarbons and oxygenated hydrocarbons from gases containing carbon monoxide and hy- .drogen in a synthesis reaction zone which comprises continuously removing a catalyst contaminated with said deposits from said fluidized solids hydrocarbon synthesis reaction zone, passing said contaminatedwcatalyst-to a hydrogenation zone, .maintaining a fluidized bed of said contaminated catalystin SaidhydrOgenation zone, passing a hydrogen-containing gas upwardly through a dense luidized bed of said contaminated solids in said zone, maintaining a temperature of from about 450 to about 750 F. V and an elevated pressure of up `to about 750 pounds per square inch gauge suitable for destructive hydrogenation at these temperatures in said zone, retaining the v,catalyst in said hydrogenation zone for a sufficient periodfof time to permit destructive hydrogenation of said deposits on said contaminated catalyst, converting in said hydrogenation Zone a portion of a said contaminants into destructive .hydrogenationvproducts volatile at said hydrogenation temperature and pressure and another portion into destructive hydrogenation products involatile at said hydrogenation temperature and pressure, said latter portion remaining on the catalyst, withdrawing from said Zone a catalyst .containing said latter portion and being more susceptible to solvent extraction than the conthesis product.

. 3. The methodset forth in claim 1 in which an amount ofY catalyst is added to the synthesis reaction zone substantially equal to that which is withdrawn. f

.4. The methodset forth in claim l in which a volatile material containing unused hydrogen is withdrawn from the hydrogenation zone, subjected to scrubbing to removev at least a portion of carbonaceous material therefrom, and said thus 6 puried hydrogen is recycled to the hyclrogena.- UNITED STATES PA'IENTS tion Zone.

5. The method set forth in claim 1 in which luslgs Peclame OctDSaelgSs catalyst is Withdrawn from the hydrogenation 1954096 Pier e-l- Apr: 10 1934 Zone and charged to a point at near the top of 6 2159140 Ecken et t1-"T"- May 23 1939 said solvent extraction zone in the form of an 2238726 Feisst et alf Aug 15: 1941 aefated column exerting pseudo-hydrostatic 2247087 Herbert --June- 24, 1941 force. 12 Y 1, 1

6. The method set forth in claim 1 in whioh 3ggg lvftton i6, g the catalyst is treated with a solvent in a. counter- 10 2:414276 Sensel Siggi-:III: Jan: 141 11947 current Operatlon 2,414,852 Burnside et al. Jan, 28, 1947 LINDSAY I. GRIFFIN, JR.

REFERENCES CITED The following references are of record in the 15 le of this patent: 

